Precipitation, Characterization, Kinetic, and Thermodynamic Modelling of Synthetic C-S-H Systems (C-S-H, CASH, CSH+$)

Maya Nicole Harris
EPFL, 2022
Thèse EPFL

Résumé

This thesis investigates the effects of aluminates, sulfates, and heterogeneous substrates on the nucleation and growth of synthetic calcium-silicate-hydrates (C-S-H) produced by dropwise precipitation. The use of synthetic C-S-H, separate from other cementitious phases, allows formation mechanisms and kinetics effects to be investigated in a simplified system. The addition of other ions and substrates then allows an approach to the more complicated, multi-phase system of cement and concrete. The first goal of this thesis was to reproducibly synthesize single-phase C-S-H with Ca:Si from 1 to 2. Guidelines were described for collection, drying, and handling of the precipitates to prevent the formation of Ca(OH)2 during synthesis and minimize carbonation. Interlayer spacing in precipitates was studied by transmission XRD to compare the effects of Ca:Si, relative humidity, and time, using the 14Å tobermorite structure as a baseline for synthetic C-S-H. The growth and nucleation kinetics of C-S-H were then investigated with the combined thermodynamic and population balance equation model (PBEM). The surface characteristics of C-S-H, C-A-S-H, and C-S-H + $were investigated by acoustophoresis to compare the effects of Ca:Si, washing, and dispersion media on zeta potential measurements. Results showed the necessity of full characterization of both solutions and precipitates in order to understand and compare acoustophoresis results. In the final section of the thesis C-S-H, C-A-S-H, and C-S-H +$ were grown on the surface of heterogeneous substrates, quartz and calcite, to approach C-S-H growth in real systems. Overall, the results from this thesis provided helpful information on synthetic C-S-H, C-A-S-H, and C-S-H + $ at the full range of Ca:Si molar ratios, particularly ratios above 1.5, as observed in Portland cement. As we get closer to understanding and controlling C-S-H in real systems, this work will help provide insight as to how heterogenous substrates and aluminates introduced by SCMs, in addition to sulfates, commonly added to cement via gypsum, affect the early age strength and kinetics of C-S-H formation.

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Maya Nicole Harris
EPFL, 2022
Thèse EPFL

Résumé

Official source

https://infoscience.epfl.ch/record/295975?ln=fr

À propos de ce résultat

Concepts associés (15)

Concepts associés

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Publications associées (13)

Publications associées

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Impact of water activity on the mineralogy of hydrated cement

Luis Guillermo Baquerizo Ibarra

Cement hydrates and their chemically bound water content are sensitive to changes in relative humidity (RH) and temperature. This may cause specific solid volume changes affecting dimensional properties of hydrated cement paste such as shrinkage, swelling and expansion, and therefore impact the performance and the transport properties of cementitious materials. The present thesis studies the impact of drying conditions on the structure and thermodynamic properties of crystalline cement hydrates in different hydration states (i.e. varying molar water contents). The cement hydrates studied include the most important AFm and AFt phases present in different types of cements. A novel multi method approach, including XRD, TGA, DSC, sorption balance measurements, sorption calorimetry and the hydrate pair ¿ humidity buffer method, was used to derive physico-chemical boundary conditions and the thermodynamic properties of the studied hydrated phases. The stability and hydration states of AFm phases depend on the anion content and the exposure conditions. Some phases such as monosulfoaluminate and hydroxy-AFm are very sensitive to different relative humidities. On the other hand monocarboaluminate and strätlingite present very good volume stability with varying RH. Ettringite shows a strong hysteresis during desorption/adsorption, and the thermodynamic properties associated with its decomposition and reformation were determined. The experimental results were included into a thermodynamic model capable of predicting the response of cementitious systems considering the ¿true¿ crystal water content on the final phase assemblage in two different scenarios: i) during hydration, even at conditions where the amount of water added was insufficient for complete hydration, and ii) during drying and re-wetting processes in already hydrated systems. Our work hence opens the possibility to model the response of various cement materials exposed to different climatic conditions and to engineer cementitious systems with respect to minimizing volume changes in the course of drying, which may positively impact properties like drying shrinkage and total porosity.

EPFL2015

Chargement

The aim of this thesis was to synthesise and control a nanostructured composite of copper/cobalt. Both the copper and cobalt oxalate exhibit a nanostructure. Attempts to produce nanocomposite particles in the size range of 10-70 nm were made via an oxalate co-precipitation route followed by the appropriate thermal treatment to finally obtain the metal nanocomposite. Much attention was focussed on the understanding of the copper oxalate precipitation and its further transformation into metal before the investigation of the co-precipitation system. One major challenge of this thesis work was to achieve a better understanding of the copper oxalate precipitation mechanism. This was made by following kinetic parameters in order to shed light on the various steps of the precipitation from a supersaturated solution (nucleation, growth and aggregation of nanocrystals). Following the pH as a function of time and using the thermodynamic solubility data it was possible to propose a kinetic model of copper oxalate precipitation, with the co-precipitation of slight amounts (around 0.40% wt) of malachite (CuCO3·Cu(OH)2). The copper oxalate nanostructured particle growth mechanism, from the self-assembly of nanosized buildings blocks, was confirmed for intermediate precipitation times (1-15 minutes). Evidence for such organisation of the particles was shown by a combination of XRD diffraction, SEM and AFM measurements showing the presence of steps at the particle surface with a height that corresponds to a multiple of the mean crystallite size in that particular crystallographic orientation. Further investigations were performed for the early steps of the precipitation by SAXS but either the precipitated volume fraction was too low for detection of the particles or nucleation and growth kinetics were to fast (less than one second) to be followed. The TEM cross-section analyses showed a possible core-shell assembly mechanism. The core showed a random organisation of the crystallites with a size of around 25 nm, while the crystallite in the shell with a size of around 40 nm presented certain order along the 110 axis, particularly towards the particle surface. All these details provided the opportunity to propose a new and more detailed mechanism of the copper oxalate polycrystalline particle formation. In order to master the conditions of the Cu/Cu oxalate decomposition, a good understanding of the simple copper oxalate decomposition was necessary. All along this thesis, much attention was paid to the transformation of the copper oxalate cubic particles into the metal. The objective was thus to conserve the particles cubic macrostructure morphology and their internal nanoscale spatial organisation. To this goaltwo routes were investigated: a direct transformation and another, an indirect one, that required the formation of an oxide. Both the copper oxalate and the oxide showed an anisotropic behaviour during the transformation into the metal. It is shown experimentally that the anisotropy, nanostructure and inhomogeneity of the initial nanocrystallites of both the oxalate and the oxide have an important influence on the mechanism and evolution of transformation into the metal. The particle morphology was shown to be lost for a transformation yield of α>0.80 in the case of the direct transformation from the oxalate whereas the morphology was kept up to the metallic state when passing via the oxide. A kinetic model was proposed for both systems using the method of the sudden change in temperature and pressure. The kinetics analysis did not permit a total understanding of the transformations studied, as several stages were shown to have complex and concurrently competing mechanisms. However, a geometrical model was proposed using the ex-situ analysis of the samples as a function of the reaction yield for both routes. For the initial stages of the copper oxide reduction under He/H2 atmospheres, the kinetic analysis showed hydrogen dissociation as a rate-limiting step. With a view to producing a cobalt/copper composite, preliminary experiments were carried out for the co-precipitation of the Co/Cu oxalate with different cationic ratios. Thermodynamic calculations showed the formation of the two solids was possible independent of the ratio Co/Cu. Experimentally, however a co-precipitation was obtained only for a ratio Co/Cu of 1, whereas for other ration only one single phase (either copper oxalate or cobalt oxalate) was formed. A second route was investigated using cobalt oxalate or cobalt oxide seeds. The amount of the cobalt detected by TEM in the precipitate using either the oxalate or from the oxide seeds was around 3%wt, which is lower than the value of 10%wt necessary to provide desired magnetic properties in the resulting precipitate. The exact nature and spatial distribution of the cobalt was not ascertained and further analysis of the nanostructure by TEM needs to be carried out to confirm the premise of the seed route. This thesis has shown that it is possible to get to a deeper understanding of the kinetics and the mechanism of the copper oxalate precipitation using the appropriate techniques. The cubic macrostructure can be conserved from the initial CuO nanoparticles (13 nm) to metallic Cu (42 nm) by a controlled transformation in a reducing atmosphere. Preliminary experiments made on the possible formation of a Co/Cu composite via the use of the cobalt oxide seeds as heterogeneous nuclei for the copper oxalate precipitation seems most promising.

EPFL2004

Chargement

Introduction aux nouveaux bilans énergétiques.

Lucien Borel

Exergy analysis of systems is extremely rich as it uses the so-called exergy accountancy which takes into account first and second principles of thermodynamics. This exergetic accountancy enables to quantitatively evaluate what is calles qualitatively the energy degradation, i.e. to calculate precisely the consequences of different phenomena of thermodynamical irreversibility, indeed to calculate correctly the thermodynamic losses in a system. Therefore the exergetic accountancy enables to define correctly a thermodynamical yield, expressing the perfection degree, i.e. the thermodynamical quality of any system. Exergy analysis is a way to estblish a true diagnosis concerning the thermodynamical health of a system of any size, any complexity, whatever phenomena may take place in it (element, apparatus, machine, plant, system). It allows to move toward a better system optimization and a more rational use of plants. Finally it is a logical and coherent stand for energy tariffing.

1989

Chargement

Impact of water activity on the mineralogy of hydrated cement

Luis Guillermo Baquerizo Ibarra

EPFL2015

EPFL2004